US2874183A - Unsaturated aldehydes and process for the preparation of such compounds - Google Patents

Unsaturated aldehydes and process for the preparation of such compounds Download PDF

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Publication number
US2874183A
US2874183A US527644A US52764455A US2874183A US 2874183 A US2874183 A US 2874183A US 527644 A US527644 A US 527644A US 52764455 A US52764455 A US 52764455A US 2874183 A US2874183 A US 2874183A
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methyl
parts
trimethylcyclohexen
aldehyde
buten
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Isler Otto
Ruegg Rudolf
Zeller Paul
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F Hoffmann La Roche AG
Hoffmann La Roche Inc
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F Hoffmann La Roche AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the starting materials of the process can be prepared as follows:
  • the iso-C -aldehyde can also be obtained by condensing 2,6,6-trimethylcyclohexanone-(l) by a Grignard reaction with Z-methyl-1-methoxy-2-oxy-butine-(3), partially hydrogenating at the triple bond the acetyleneglycol obtained and dehydrating .the ethylene'glycol formed and treating it with acid.
  • the initial aldehyde is converted into an enolester.
  • the starting material can be treated with lower aliphatic carboxylic acid anhydrides in the presence of acid condensation agents such as p-toluenesulfonic acid, zinc chloride, etc., or of alkalior alkali-earth salts of the corresponding acids.
  • the initial aldehyde can also be treated in the presence of acid condensation agents with an enolester of a ketone having a lower boiling point than the initial aldehyde, in which connection, by the continuous removal of the ketone from the reaction mixture, the enolester of the initial aldehyde is produced.
  • the iso-C or retrodehydro-C or iso-C or retrodehydro-C -alder hyde respectively is heated with acetic anhydride in the presence of p-toluenesulfonic acid or sodium acetate, or is heated at to C.
  • the second step of the process in accordance with the invention consists in hydrolyzing the enolesters of the initial aldehydes under mild conditions. This is done in the known manner in an aqueous medium.
  • an aqueous medium For this purpose there are particularly well suited the alkali and alkaliearth hydroxides, -carbonates or -bicarbonates.
  • a watermiscible solvent such as methyl alcohol, ethyl alcohol, dioxane, etc., can be added to the reaction mixture in order to obtain a homogeneous reaction mixture.
  • enolesters are preferably boiled for 10 to 15 hours with sodium bicarbonate in 90% aqueous methyl alcohol.
  • the aldehydes obtained in accordance with the present process are distillable oils which have characteristic absorption maxima in the ultraviolet spectrum.
  • the B-C -aldehyde and the fi-C -aldehyde are valuable intermediates for the synthesis of vitamin A and B-carotene.
  • the fi-dehydro-C -aldehyde and the ,S-dehydro-C -aldehyde are intermediates for the synthesis of Vitamin A; and of carotenoids (see copending applica- The tion Ser. No. 553,214, filed-December 15, 1955 and now abandoned).
  • Example 2 ENOLACETATE O13 RETRODEHYDRO-Cn-ALDEHYDE A mixture of 10 parts by weight 2,6,6-trimethylcyclohexen-(Z)-ylidene-acetaldehyde, parts by volume acetic anhydride and 01 part by weight p-toluenesulfonic acid are heated at 95 C. for 90 minutes. Thereupon it is cooled to 20 to 30 C. and poured into amixture of 20 parts by weight ice and 30 parts by volume water. The oily reaction product is extracted with petroleumethcr, washed with sodium bicarbonate solution and with water and dried over sodium sulfate. After the concentration of the petroleum-ether solution, the residue is distilled in vacuum.
  • n l.499; ultraviolet absorption maximum E ⁇ 3 15 (in. petroleum-ether solution)
  • Example 3 "'ENOLACETATE OF ISO-Cn-ALDEHYDE 9 parts by weight 4-[2',6',6'-trimethylcyclohexylidene]- 2-methyl-buten-(2)-al-( 1) are heated with 6.5 parts by volume isopropenylacetate and 0.045 part by Weight ptoluenesulfonic acid for 3 hours at 110 to C., the acetone produced being sloWl-y distilled otf from the reaction-mixture. After cooling, the reaction solution is poured into a mixture of 10 parts by weight of ice and 10 parts by volume of water.
  • the reaction product is extracted with petroleum-ether, the petroleum-ether solution is washed with sodium bicarbonate solution and with water and dried over sodium sulfate. After the solvent has been distilled off, there are obtained 10.4 parts by weight of crude 4-[2',6,6-trimethylcyclohexen-(l')-yl]- Z-methyl-I acetoXy-butadiene-( 1,3), which is sufficiently pure for the further treatment.
  • Example 4 B-DEHYDRO-Cu-ALDEHXDE 136 .parts by Weight 4-[2,6',6-trirnethylcyclohexen- (2)-ylidene]-2-methyl-buten-(2)-al-(l) are heated with 97 parts by volume isopropenyl acetate and 0.7 parts by weight p-toluenesulfonic acid for 3 to 4 hours at 100 to 140 C. while passing through a weak stream of nitrogen, the acetone released being continuously distilled out of the reaction mixture. Thereupon it is allowed 'to cool.
  • a process which comprises reacting a member of the group' consisting of 2,6,6-trimethylcyclohexylidenea'cetaldehyde, 2,6,6-trimethylcyclohexen-(2)-ylidene-acetaldehyde, 4-[2,6',6 trimethylcyclohexylidene] 2-met hyl buten (2) al (1) and 4-[2',6',6'-trimethylcyclohexen-( 2)-ylidene]-2-methyl-buten-( 2 -al-(l with a member of the group consisting of lower aliphatic carboxylic acid anhydride and enol ester of a'ketone having a lower boiling point than the starting aldehyde in the presence of an acid condensation agent to produce, respectively, a member of the group consisting of 2 [2,6',6 trimethylcyclohexen (1) yl] 1- acyloxy ethylene, 2 [2,6,6' trimethylcyclohexadien (1,3)
  • a process which comprises hydrolyzing 2-[2,6',6- trimethylcyclohexen-(l')-yl]-l-acyloxy-ethylene in aqueous medium under mild conditions to produce 2,6,6-trimethylcyclohexen-( 1 -ylacetaldehyde.
  • a process which comprises hydrolyzing 2-[2,6',6'- trimethylcyclohexadienl ,3 -yl] -1-acyloxy-ethy1ene in aqueous medium under mild conditions to produce 2,6,6- trimethy1cyc1ohexadien-( 1,3 -yl-acetaldehyde.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US527644A 1954-08-16 1955-08-10 Unsaturated aldehydes and process for the preparation of such compounds Expired - Lifetime US2874183A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069460A (en) * 1958-12-19 1962-12-18 Bayer Ag Process for the production of alpha, beta-unsaturated acids of the vitamin a series
US3869517A (en) * 1971-04-28 1975-03-04 Rhodia Process for preparing hydroxy citronellal by saponification of the hydroxy ester
US3917713A (en) * 1971-04-28 1975-11-04 Rhodia Process for preparing hydroxy citronellal

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE638940C (de) * 1935-05-11 1936-11-25 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von Safranal
US2466737A (en) * 1944-06-06 1949-04-12 Carbide & Carbon Chem Corp Acylations with enol esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE638940C (de) * 1935-05-11 1936-11-25 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von Safranal
US2466737A (en) * 1944-06-06 1949-04-12 Carbide & Carbon Chem Corp Acylations with enol esters

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069460A (en) * 1958-12-19 1962-12-18 Bayer Ag Process for the production of alpha, beta-unsaturated acids of the vitamin a series
US3869517A (en) * 1971-04-28 1975-03-04 Rhodia Process for preparing hydroxy citronellal by saponification of the hydroxy ester
US3917713A (en) * 1971-04-28 1975-11-04 Rhodia Process for preparing hydroxy citronellal

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NL91000C (enExample)

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